New naphthalene derivatives and their application in dye preparations



Patented Sept. 30, 1930 WILFRID ernsoN, ANTHONY JAIVLES1HAIIJWOOD, JOSEPH BARON"\IPAYMAN, AND'A Nonn SHEPHERDSON, oF' BLAoKLEY, MANCHESTER ENGLAND, AssIeNons "r mrnnmncimnr cnn rnncs'rn ns LIMITED,'V0FL01 \ID0N, ENGLAND NEW nnnrvn'riviusiann THEIR: APPLICATION DYE PREPARATIONS No'nrawing. Application med nu usti, :1928, .Serial No. 296,859, and in Great Britain August 29, 1927.

disadvantage commonlymet with aqueous pastes ofmore or less finely divided material is the tendency to coagulate and settle, so that the paste after- ,beinglrept for a a longeriorshonter time isno glenger unifarm in composition. 'Ihe additionpf gums and.

other similar thickening material has been P p a sai an the 'li ve eilx nn p c drawbacks such asliajbi-lity to attack by fungi. m We have nowdiscoveredthatpolych lorinated .naphthalenesulphonifc acid and its salts have especially valuable, properties in this connection. The addition 10f 32% of sodium polychloronaphthalenesulphonate ;(calculated on the total-Weight of'palste) tojan ,aqueous pasteoffduranthrene golden orange Y,

for example, entirely prevents the settlingout of the solid dystulf, and the pasteis found to be practically uniform in composition after am standing for a long period of time. This eifect is due to the formation of a stiff gel, which however is easily stirrable and thins rapidly when stirred or shaken.

Solutions or pastes containing polychloro- 5 naphthalenesulphonic acid or its salts are not 'liable to deterioration by fungus growths. Our products have also valuable wetting-out properties.

As long ago as 1849 Laurent (Liebigs Annalen, 72, 300) recorded the fact that the potassium salt of sulphonated tetrachloronaphthalene, when precipitated by water from its alcoholic solution, forms a gel, but hitherto no technical application of this property has been made, and no other salts have been prepared.

The compounds we use are made by sulphonation of a polychloronaphthalene containing 3 to 4.5 atoms of chlorine in the mole- ,aqpule, such as may be obtained by various known methods, particularly by the process described in British application N 0. 291,849 filed, March 4, 1927 British Dyestuffs Corp. Ltd.,Payman and Gi son).

In the examples below we describe preferred methods of sulphonation and of applying products, but our invention is not limited to the details there given, either of the particular sulphonating agent used in W'Example 1 or of the exact proportions of ties.

the reagents in any of the examples, The partsaretby weigh naphthalenesulph'onic a 0 i (Z s.-Polychloro-. V

naphthalenesulphonic acids maybe prepared from the corresponding polych-loronaphthm lene. The latter-compounds. are conveniently prepared by themethod described in British application No.i291,849, filed March 4, 1927, which method consists essentially in the direct chlorination (of melted naphthalene at temperatures between 150 andfl609C.

30O parts of'such a polychloronaphthalene,

containing approximately 3.5. atomsv of chlori-ne per molecule, areheated to 150 Ci and 300 parts of 2-2% -oleu-m are added during minutes at'150-160' fG. 1 The temperature is then raisedto 180C. and aftjer one hour at 189 O. the:mixtnre-is poured into 3000 parts, of boiling saturatedsalt solution-and allowed to cool, with stirring, for 18 hours QElieprecip-itated sodium salt is filtered olf, washed with brine, pressedwand dried .at 120 C. Unchanged; polychwloronaphthalene imay be removed by extraction with hotbenzene, and the residual sodium-salt may be freed from sodiumchloride'by washing "with 350 parts of-boi'lingwater. a 4

The product so obtained gives a'clearsold' tion inhot water; a 1.6%solution on cooling sets'to a gel, which, however,-fliquefies"when stirred for shaken dilute solutions froth readily and exhibit marked wetting-out. proper- Other salts may. be made by neutralizing the sulphonation: product with an appropriate base or salt. l

Eaample a-gTo: 100 parts of 12.5% paste. of duranthrene golden orange Y, parts" of a hot aqueous 10% solutio-lr ofz sodium trichloronaphthalene sulphonate, obtainedin the manner shown in Example l, frompoly- 1 chloronaphthalene containing atoms" of chlorine per molecule, areadded. The whole is well stirred'an-d 'allowedlto cool; 7 The product isthen ready forstoragewithout-ri'sk of settling. V

EmampZe 5."50 parts of a hotaqueous solution of sodium trichloronaphthalene sulphonateof 10% "strength aremixed with 200 parts of an aqueous paste of thioindigo in a fine state of division, containing 25% of the pure dyestufi. The mixture is thoroughly agitated and then allowed to 0001, after which it may be stored.

Example 4.20O parts of an aqueous paste of the dyestufi obtained by coupling 112:4- dinitroaniline with B-naphthol, containing 25% pure dyestufl are mixed with parts of a hot aqeuous 10% solutionofsodium trichloronaphthalene sulphonate and the mass allowed to cool; whereupon a paste essentially free from the disadvantage of settling isobtained. I

lVhat we claim and desire to secure by Letters Patent is 1. The process of manufacturing alkali metal polychloronaphthalene sulphonates which comprises heating the corresponding k polychloronophthalene with fuming sulphu ric acid, diluting the reaction products with a concentrated alkali metal salt solution, cooling and filtering oil the precipitated alkali metal salt of the polychloronaphthalene sulphonic acid;

2. The process of manufacturing alkali metal polychloronaphthalene sulphonates, which comprises heating a polychloronaphthalene, containing from 3 to 4.5 atoms of chlorine in the molecule, with fuming sulphuric acid, diluting the reaction products with a concentrated alkali'metal salt solution, cooling and filtering oi? the precipitated alkali metal salt of the polychloronaphthalene sulphonic acid. r

3. The process of manufacturing alkali metal polychloronaphthalene sulphonates which comprises heating the corresponding polychloronaphthalene with fuming sulphuric acid, diluting the reaction products with a concentrated alkali metal salt solution, cooling, filtering off the precipitated alkali metal salt of the polychloronaphthalene sulphonic acid and recovering the un- ,changed polychloronaphthalene by an extraction with benzene.

' 4. In the process of producing alkali metal poylchloronaphthalene sulphonates from polychloronaphthalene, the step which comprises the recovery of the unchanged polychloronaphthalene by an extraction of the mother liquor with benzene. i

5. The process of manufacturing sodium polychloronaphthalene sulphonate, which comprises heating a polychloronaphthalene containing from 3 to 4.5 atoms of chlorin in the molecule with fuming sulphuric acid, di luting the reaction products with a concentrated solution of sodium chloride, cooling and filtering off the precipitated sodium salt of the polychloronaphthalene sulphonic acid.

6. A process of manufacturing an alkali metal polychloronaphthalene sulphonate, which consists in heating a polychloronaphthalene with about 22 per cent of fuming sulphuric acid at a temperature of about 150 0., raising the temperature and holding it at about 180 C. for approximately an hour, diluting the solution with a large volume of saturated alkali metal salt solution, cooling and filtering off the precipitated alkali metal salt1 of the polychloronaphthalene sulphonic aci 7. As a new composition of matter asodium polychloronaphthalene sulphonate, containing from 3 to 4.5 atoms of chlorin to the molecule, which is soluble in hot water producing a clear solution which, at concentrations above about 1 to 5 per cent, sets on 

